Process for the production of crystalline silicate ISI-4 using ethylene glycol

ABSTRACT

Crystalline silicates and processes for the production thereof are described. These crystalline silicates are of new crystalline structure, which, as determined after calcination in the air at 550° C., have a composition represented by the general formula (I): pM 2/n  O.Al 2  O 3 .qSiO 2  (the symbols are as defined in the appended claims) and give a X-ray diffraction pattern as shown in Table 2. They are superior in heat resistance and acid resistance, and can be used as catalysts for the conversion of various organic compounds, absorbents, or as catalysts for various reactions. They are produced by reacting an aqueous mixture comprising (a) a silica source, (b) an alumina source, (c) an alkali metal and/or alkaline earth metal source, and (d) ethylene glycol or (e) monoethanolamine at a temperature of 100° to 300° C. till the desired crystalline silicates are formed. Although ethylene glycol and monoethanolamine do not remain in the crystalline silicates, they play important roles in the formation of the desired crystalline structure in the course of the production thereof.

This application is a division of application Ser. No. 512,996 filedJuly 12, 1983, now abandoned.

BACKGROUND OF THE INVENTION

The present invention relates to crystalline silicates of novelstructure and a process for the production of said crystallinesilicates. More particularly, the present invention relates tocrystalline silicates having a novel structure which can be effectivelyused as catalysts for various chemical reactions, and also to a processfor efficiently producing said crystalline silicates. These crystallinesilicates are called herein crystalline silicates (ISI-4).

A number of crystalline silicates, natural or synthetic, have heretoforebeen known, and various processes for the production thereof have beenproposed. In general, these crystalline silicates are produced bypreparing an aqueous mixture consisting of a silica source, an aluminasource, and an alkali metal source and, thereafter, subjecting theaqueous mixture to a hydrothermal reaction.

Recently, a method has been developed to produce crystalline silicatezeolites with a specific structure by adding organic compoundsexemplified by tetrapropylammonium bromide to the aqueous mixture. Forexample, Japanese Patent Application Laid-Open No. 134517/81 describesthat ZSM-5 zeolite is produced by adding diols to the aqueous mixture.Also, Japanese Patent Application Laid-Open No. 107499/79 describes thatcrystalline aluminosilicate zeolites with specific structure areproduced by adding monoethanolamine. Although the structure is notshown, examination of the examples of Japanese Patent ApplicationLaid-Open No. 17920/81 in which nearly the same conditions as inJapanese Patent Application Laid-Open No. 107499/79 are employed revealsthat the crystalline aluminosilicate zeolites are similar to ZSM-5zeolite.

As a result of extensive investigations to develop silicates with anovel composition and a novel crystalline structure, it has been foundthat, although organic compounds such as monoethanolamine are added insmall amounts in relation to the silica source or alumina source inconventional methods, if ethylene glycol or monoethanolamine of theorganic compounds is added in such a large amount as to be a solvent,crystalline silicates with a novel structure are obtained.

SUMMARY OF THE INVENTION

The present invention provides:

(1) a crystalline silicate named as "ISI-4" having a composition, asdetermined after calcination in the air at 550° C., represented by thegeneral formula (I):

    pM.sub.2/n O.Al.sub.2 O.sub.3.qSiO.sub.2                   (I)

(wherein M represents at least one element selected from hydrogen,alkali metals and alkaline earth metals, n represents the valence of M,and p and q each represents a molar ratio and is chosen within theranges of 0.3≦p≦3.0 and q≧10) and giving a principal X-ray diffractionpattern, also as determined after calcination in the air at 550° C., asshown in Table 1 as described hereinafter;

(2) a process for producing the crystalline silicate as defined in (1)above, which comprises reacting an aqueous mixture comprising (a) asilica source, (b) an alumina source, (c) an alkali metal and/oralkaline earth metal source, and (d) ethylene glycol in the followingmolar ratios:

silica/alumina≧10/1,

ethylene glycol/water=0.05/1 to 10/1,

ethylene glycol/silica=2/1 to 100/1,

hydroxyl ion/silica=0.01/1 to 0.5/1 (excluding hydroxyl ions resultingfrom organic bases) at a temperature of 100° to 300° C. till the desiredcrystalline silicate is formed; and

(3) a process for producing the crystalline silicate as defined in (1)above, which comprises reacting an aqueous mixture comprising (a) asilica source, (b) an alumina source, (c) an alkali metal and/oralkaline earth metal source, and (e) monoethanolamine in the followingmolar ratios:

silica/alumina≧10/1,

monoethanolamine/water=0.05/1 to 10/1,

monoethanolamine/silica=2/1 to 100/1,

hydroxyl ion/silica=0.01/1 to 0.5/1 (excluding hydroxyl ions resultingfrom organic bases) at a temperature of 100° to 300° C. till the desiredcrystalline silicate is formed.

                  TABLE 1                                                         ______________________________________                                        Lattice Spacing d (Å)                                                                      Relative Intensity                                           ______________________________________                                        11.31 ± 0.2   strong                                                       10.92 ± 0.2   very strong                                                  7.83 ± 0.2    medium                                                        4.51 ± 0.15  very strong                                                  4.24 ± 0.1    strong                                                       3.89 ± 0.1    strong                                                       3.73 ± 0.1    medium                                                       3.69 ± 0.1    very strong                                                  3.61 ± 0.1    very strong                                                   3.53 ± 0.07  medium                                                        3.43 ± 0.07  strong                                                        2.52 ± 0.05  medium                                                       ______________________________________                                         Irradiation: Cu--K.sub.α                                                Wavelength: 1.5418                                                       

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE shows an X-ray diffraction pattern of the crystallinesilicate (ISI-4) obtained in Example 1 as described hereinafter. In theFIGURE, θ means the angle of the incidence.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the present invention, (a) a silica source, (b) analumina source, (c) an alkali metal and/or alkaline earth metal source,and (d) ethylene glycol or (e) monoethanolamine are added to water toprepare an aqueous mixture, and the aqueous mixture is then reacted tillthe desired crystalline silicate is formed.

The silica source (a) as used herein is not critical, and silica powder,silicic acid, colloidal silica, dissolved silica, etc. can be used.Examples of such dissolved silicas include water glass silicate andalkali metal silicate, containing 1 to 5 moles of SiO₂ per mole of Na₂ Oor K₂ O.

As the alumina source (b), various compounds can be used, includingaluminum sulfate, sodium aluminate, colloidal alumina, and alumina.

The ratio of silica to alumina in the aqueous mixture can be determinedappropriately. The molar ratio of silica (SiO₂) to alumina (Al₂ O₃) ispreferably at least 10:1, and the optimum molar ratio is from 40:1 to1,000:1.

As the alkali metal and/or alkaline earth metal source (c), variouscompounds can be used. For example, sodium hydroxide, potassiumhydroxide, etc. can be used as the alkali metal source. Sodium silicateand sodium aluminate serve also as the silica source and the aluminasource, respectively. A particularly preferred alkali metal is sodium.As the alkaline earth metal source, calcium nitrate, calcium chloride,etc. can be used.

The molar ratio of alkali metal and/or alkaline earth metal to silica inthe aqueous mixture is not critical and can be determined appropriatelydepending on various conditions. It is usually from 0.05:1 to 6:1 andparticularly preferably from 0.1:1 to 3:1.

Ethylene glycol (d) does not remain in the ultimate crystallinesilicate, but plays an important role in forming the desired crystallinestructure in the course of the production thereof. It is preferred thatethylene glycol be used in relatively large amounts. For example, themolar ratio of ethylene glycol to water is from 0.05:1 to 10:1 andparticularly preferably from 0.1:1 to 5:1, and the molar ratio ofethylene glycol to silica is from 2:1 to 100:1 and particularlypreferably from 4:1 to 10:1. In the present invention, monoethanolamine(e) can be used in place of ethylene glycol (d). Monoethanolamine (e)plays the same role as ethylene glycol (d). Also with regard to theamount of monoethanolamine being added, it is preferred to be used inrelatively large amounts. For example, the molar ratio ofmonoethanolamine to water is from 0.05:1 to 10:1 and particularlypreferably from 0.1:1 to 5:1, and the molar ratio of monoethanolamine tosilica is from 2:1 to 100:1 and particularly preferably from 4:1 to10:1.

In the aqueous mixture prepared by adding the foregoing components (a),(b), (c), and (d) or (e) to water, the molar ratio of hydroxyl ion tosilica should be adjusted to from 0.01:1 to 0.5:1. In this case, themoles of hydroxyl ions are calculated excluding those ions resultingfrom the addition of organic bases such as monoethanolamine.

The aqueous mixture is reacted by heating under the condition, e.g.,temperatures and perids of time, that are required for forming thedesired crystalline silicate (ISI-4). In more detail, it is sufficientfor the aqueous mixture to be heated at a temperature of from 100° to300° C., preferably from 120° to 200° C. for a period of time of from 5hours to 10 days, preferably from 10 hours to 5 days. There is nospecial limitation to the pressure at which the reaction is performed.Usually the reaction is performed at autogenous pressure. The reactionis usually performed while stirring and, if necessary, may be performedin an inert gas atmosphere. Although the pH of the reaction system isnot critical, it is preferred to be adjusted to at least 7.5, with therange of from 7.5 to 12.0 being particularly preferred.

It is required for the reaction of crystallization to be performedalways in the presence of ethylene glycol or monoethanolamine. Unlessthis requirement is satisfied, the desired crystalline silicate (ISI-4)cannot be obtained. In this reaction, there is no special limitation tothe order in which the components are mixed. In a preferred embodiment,an aqueous aluminum salt solution, an aqueous silicate solution, and anaqueous alkali metal salt and/or alkaline earth metal salt solution areadded dropwise concurrently to water and mixed and, thereafter, ethyleneglycol or monoethanolamine is added to the mixture.

After the crystallization reaction is completed, the resulting reactionmass is washed with water and dried at about 120° C. and then iscalcined in the air at 550° C. for 6 hours, whereby there can beobtained the crystalline silicate (ISI-4) having a compositionrepresented by the general formula (I) and giving a principal X-raydiffraction pattern as shown in Table 1.

Relative intensities of lattice spacings other than the principallattice spacings shown in Table 1 are not critical in the crystallinesilicate (ISI-4) of the invention. Preferred, however, are thosecrystalline silicates giving an X-ray diffraction pattern as shown inTable 2 below.

                  TABLE 2                                                         ______________________________________                                        Lattice Spacing d (Å)                                                                      Relative Intensity                                           ______________________________________                                        11.31 ± 0.2   strong                                                       10.92 ± 0.2   very strong                                                  10.03 ± 0.2   weak                                                         7.83 ± 0.2    medium                                                        6.08 ± 0.15  weak                                                          5.61 ± 0.15  weak                                                          5.24 ± 0.15  weak                                                          4.90 ± 0.15  weak                                                          4.51 ± 0.15  very strong                                                  4.42 ± 0.1    weak                                                         4.24 ± 0.1    strong                                                       4.14 ± 0.1    weak                                                         3.89 ± 0.1    strong                                                       3.73 ± 0.1    medium                                                       3.69 ± 0.1    very strong                                                  3.61 ± 0.1    very strong                                                   3.53 ± 0.07  medium                                                        3.43 ± 0.07  strong                                                        3.32 ± 0.07  weak                                                          3.16 ± 0.07  weak                                                          2.97 ± 0.07  weak                                                          2.83 ± 0.05  weak                                                          2.52 ± 0.05  medium                                                       ______________________________________                                         Irradiation: Cu--K.sub.α                                                Wavelength: 1.5418                                                       

The relative intensity was determined as shown below with the intensityat the lattice spacing of 10.92±0.2 Å as 100%.

    ______________________________________                                        Very strong:    70 to 100%                                                    Strong:        50 to 70%                                                      Medium:        30 to 50%                                                      Weak:           0 to 30%                                                      ______________________________________                                    

The crystalline silicate (ISI-4) of the present invention is a silicatehaving a new crystalline structure and shows superior heat resistanceand acid resistance and, therefore, can be used, for example, as acatalyst for use in the reaction of conversion of various organiccompounds, an absorbent, and a catalyst for various reactions. When thecrystalline silicate (ISI-4) is used as a catalyst, for example,hydrocarbons can be produced from oxygen-containing compounds obtainedfrom coal, biomass, etc. by a simplified process and moreover in a highconversion over a long period of time. Also, when the crystallinesilicate (ISI-4) is used as a catalyst, liquid hydrocarbons having largeamount of aromatic components can be efficiently produced fromhydrocarbons having small amount of aromatic components.

Oxygen-containing compounds which can be used in the production ofhydrocarbons include compounds containing from 1 to 4 carbon atoms, suchas alcohols, ethers, aldehydes, and carboxylic acids. In more detail,methanol, ethanol, propanol, butanol, dimethyl ether, diethyl ether,acetaldehyde, propylaldehyde, acetic acid, propionic acid, etc. can beused. Of these compounds, methanol is particularly preferred. Productionof hydrocarbons from such oxygen-containing compounds can be carried outby contacting the oxygen-containing compounds with the crystallinesilicate (ISI-4) catalyst. The production reaction is carried out atatmospheric pressure or under pressure. As for other conditions of thereaction, the temperature is from 250° to 600° C. and preferably from300° to 500° C., and the weight hourly space velocity (WHSV) is from 0.1to 50 per hour and preferably from 0.5 to 10 per hour. This reactionenables to produce olefins of high practical value, particularlyethylene, propylene and butene, from oxygen-containing compoundsobtained from feedstocks other than oil, such as coal and biomass, in ahigh selectivity. In addition, xylene can be produced, in which thep-xylene content is very high. Moreover, hydrocarbons such as butane canbe produced efficiently.

In efficiently producing the foregoing liquid hydrocarbons having largeamount of aromatic components, as described above, hydrocarbons havingsmall amount of aromatic components are used as feedstocks. There is nospecial limitation to the type of hydrocarbon used as feedstocks.Moreover, the aromatic component content in the hydrocarbons is notcritical, but those hydrocarbons having an aromatic component content of15% by weight or less are usually employed. Examples of such hydrocarbonfeedstocks are naphtha fractions such as a light naphtha and a heavynaphtha. Particularly suitable are fractions having a number of carbonatoms of at least 4 and a boiling point of 200° C. or lower, especiallythose fractions having a number of carbon atoms of at least 4 and aboiling point of 140° C. or lower. In addition, olefins or paraffinscontaining from 2 to 4 carbon atoms can be used alone or in combinationwith each other and moreover in mixture with the foregoing naphthafraction. In particular, it is preferred to use a mixture of theabove-described naphtha fraction and olefin containing from 2 to 4carbon atoms. In this case, when the weight ratio of olefin to naphthafraction is adjusted to 0.05:1 to 19:1, with the weight ratio of from0.18:1 to 5.7:1 being particularly preferred, there are produced liquidhydrocarbons having large amount of aromatic components as compared withthe case in which they are used separately; that is, the so-calledsynergistic effect can be obtained. This reaction is usually carried outat a pressure of from atmospheric pressure to 50 kilograms per squarecentimeter by gauge, preferably from atmospheric pressure to 20kilograms per square centimeter by gauge, a temperature of from 200° to550° C., preferably from 300° to 500° C., and a weight hourly spacevelocity (WHSV) of from 0.1 to 50 per hour, preferably from 0.5 to 10per hour. In accordance with this reaction, liquid hydrocarbons havinglarge amount of aromatic components and of very high practical value,such as a gasoline fraction, can be produced very efficiently from thosehydrocarbons having small amount of aromatic components and lowpractical value. Light gases as by-product herein can be recycled andused as hydrocarbon feed-stocks.

Thus the crystalline silicate (ISI-4) of the invention can be usedwidely in oil refinery, production of gasoline, or in various chemicalindustries.

The present invention is described in greater detail by reference to thefollowing examples.

EXAMPLE 1

Solution A consisting of 7.52 grams of aluminum sulfate (18 hydrates),17.6 grams of sulfuric acid (97%) and 100 milliliters of water, andSolution B consisting of 211 grams of water glass (SiO₂ : 29.0% byweight, Na₂ O: 9.4% by weight, water: 61.6% by weight) and 46milliliters of water were prepared. Solutions A and B were graduallyadded dropwise to 100 milliliters of water at the same time and mixed.Then, 6 grams of sulfuric acid (50%) was added, and the resultingmixture was adjusted to pH 9.5. In addition, 376 milliliters of ethyleneglycol was added thereto and mixed. The thus-prepared aqueous mixturewas then placed in a one-liter autoclave and reacted with stirring at170° C. and autogenous pressure for 20 hours.

The reaction mixture was cooled and, thereafter, washed five times with1.5 liters of water. It was then filtered, and the resulting solid wasdried at 120° C. for 6 hours to obtain 55.0 grams of crystallinesilicate. Then it was calcined in the air at 550° C. for 6 hours. Thusobtained crystalline silicate had a composition (expressed in a molarratio) of 0.9Na₂ O.Al₂ O₃.74.OSiO₂, and gave an X-ray diffractionpattern as shown in the FIGURE.

EXAMPLE 2

The procedure of Example 1 was repeated with the exception thatmonoethanolamine was used in place of ethylene glycol. The thus-obtainedcrystalline silicate had the same composition and X-ray diffractionpattern as in Example 1.

EXAMPLE 3

Solution A consisting of 1.85 grams of sodium aluminate, 7.2 grams ofsodium hydroxide (95%) and 236 milliliter of water, and Solution Bconsisting of 200 grams of colloidal silica (SiO₂ : 30% by weight,water: 70% by weight) were prepared. Solutions A and B were graduallyadded dropwise at the same time and mixed. The thus-prepared mixture wasreacted, and then washed and dried in the same manner as in Example 1 toobtain 52.0 grams of crystalline silicate. The composition (expressed ina molar ratio) of the crystalline silicate was 0.8Na₂ O.Al₂ O₃.76.OSiO₂.

APPLICATION EXAMPLE 1

The crystalline silicate (ISI-4) produced in Example 1 was subjected toan ion exchange reaction at room temperature for one day and night with5 milliliters of 1 normal ammonium nitrate per gram of the crystallinesilicate. The crystalline silicate was then washed with pure water anddried at 120° C. and, thereafter, calcined at 550° C. for 6 hours in theair to produce a H-type silicate. To this H-type was added an aluminasol in the amount (calculated as alumina) of 35% by weight, and theresulting mixture was extrusion-molded and calcined at 550° C. for 6hours in the air to obtain a catalyst.

The thus-produced catalyst (2.5 grams) was placed in a flow typereactor, with which methanol was contacted for 4 hours under theconditions of atmospheric pressure, 370° C., and WHSV=2.0 per hour whilepassing it through the reactor. The results are shown in Table 3.

COMPARATIVE EXAMPLE 1

Crystalline aluminosilicate ZSM-34 (1.0 gram, produced by the proceduredisclosed in Japanese Patent Application Laid-Open No. 58499/78) wascharged to a flow type reactor, with which methanol was contacted for5.5 hours under the conditions of atmospheric pressure, 371.1° C., andWHSV=3.0 per hour while passing it through the reactor. The results areshown in Table 3.

                  TABLE 3                                                         ______________________________________                                                         Application                                                                           Comparative                                                           Example 1                                                                             Example 1                                            ______________________________________                                        Conversion of Methanol (%)                                                                       93.5      85.9                                             Hydrocarbon                                                                   Composition (wt %)                                                            Methane            1.8       2.3                                              Ethane             0.2       0                                                Ethylene           16.7      25.9                                             Propane            2.6       2.1                                              Propylene          17.6      17.6                                             Butane             15.3      1.9                                              Butene             13.7      5.4                                              Hydrocarbons containing                                                                          32.2      45.1                                             5 or more carbon atoms                                                        (C.sub.5.sup.+)                                                               Composition of Xylene* (wt %)                                                 p-Xylene           83.5      --                                               m-Xylene           10.8      --                                               o-Xylene           5.8       --                                               ______________________________________                                         *The isomer composition of xylene contained in hydrocarbons containing 5      or more carbon atoms is shown. The xylene content of the hydrocarbons         containing 5 or more carbon atoms was 11.9% by weight.                   

APPLICATION EXAMPLE 2

The same catalyst as used in Application Example 1 was charged to a flowtype reactor, with which olefin-containing gas with the compositionshown in Table 4 was contacted under the conditions of atmosphericpressure, 450° C., and WHSV=1.0 per hour while passing it through thereactor. The results are shown in Table 6.

APPLICATION EXAMPLE 3

The procedure of Application Example 2 was repeated with the exceptionthat liquid hydrocarbon with the composition shown in Table 5 was usedas a hydrocarbon feedstock in place of the olefin-containing gas. Theresults are shown in Table 6.

APPLICATION EXAMPLE 4

The procedure of Application Example 2 was repeated with the exceptionthat a 30:70 (by weight) mixture of the olefin-containing gas of thecomposition shown in Table 4 and the liquid hydrocarbon of thecomposition shown in Table 5 was used as a hydrocarbon feedstock inplace of the olefin-containing gas. The results are shown in Table 6.

APPLICATION EXAMPLE 5

The procedure of Application Example 2 was repeated with the exceptionthat a 50:50 (by weight) mixture of the olefin-containing gas of thecomposition shown in Table 4 and the liquid hydrocarbon of thecomposition shown in Table 5 was used as a hydrocarbon feedstock inplace of the olefin-containing gas. The results are shown in Table 6.

                  TABLE 4                                                         ______________________________________                                        Component      Proportion (wt %)                                              ______________________________________                                        Ethane         0                                                              Ethylene       0                                                              Propane        0.2                                                            Propylene      0.1                                                            iso-Butane     38.0                                                           n-Butane       6.7                                                            l-Butene       14.7                                                           iso-Butene     33.4                                                           trans-2-Butene                                                                cis-2-Butene   6.9                                                            C.sub.5.sup.+  0.1                                                            ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        Component        Proportion (wt %)                                            ______________________________________                                        Butane           2.9                                                          iso-Pentane      16.3                                                         n-Pentane        28.5                                                         n-Hexane         16.5                                                         Other C.sub.6.sup.+  compounds                                                                 35.8                                                         ______________________________________                                    

                                      TABLE 6                                     __________________________________________________________________________                    Application                                                                          Application                                                                          Application                                                                           Application                                             Example 2                                                                            Example 3                                                                            Example 4                                                                             Example 5                               __________________________________________________________________________    Reaction Conditions                                                           Pressure        atmospheric                                                                          atmospheric                                                                          atmospheric                                                                           atmospheric                                             pressure                                                                             pressure                                                                             pressure                                                                              pressure                                Temperature (°C.)                                                                      450    450    450     450                                     WHSV (hr.sup.-1)                                                                              1.0    1.0    0.3 + 0.7*.sup.1                                                                      0.5 + 0.5*.sup.1                        Conversion of Butene (%)                                                                      91.3   --     92.1    93.1                                    Reaction Results                                                              Methane (wt %)  0.9    0.0    0.4     0.5                                     Ethane + Ethylene (wt %)                                                                      1.6    1.1    1.3     1.2                                     C.sub.3 (Propylene) (wt %)                                                                    9.3 (2.9)                                                                            18.5 (1.3)                                                                           14.2 (1.1)                                                                            14.6 (1.5)                              C.sub.4 (butene) (wt %)                                                                       72.3 (4.8)                                                                           49.5 (3.1)                                                                           58.0 (4.3)                                                                            60.8 (3.7)                              C.sub.5.sup.+ (wt %)                                                                          15.9   30.9   26.1 (26.4)*.sup.2                                                                    22.9 (23.5)*.sup.2                      Aromatic Fraction/C.sub.5.sup.+ (wt %)                                                        68.3   25.1   41.3 (32.9)*.sup.2                                                                    51.2 (39.6)*.sup.2                      __________________________________________________________________________     *.sup.1 The lefthand figure indicates the WHSV of the olefincontaining        gas, and the righthand figure indicates the WHSV of the liquid                hydrocarbon.                                                                  *.sup.2 Expected values on basis of the results of Application Examples 2     and 3.                                                                   

What is claimed is:
 1. A process for producing a crystalline silicate,when determined after calcination in the air at 550° C., having acomposition represented by the general formula (I),

    pM.sub.2/n O.Al.sub.2 O.sub.3.qSiO.sub.2                   (I)

wherein M represents at least one element selected from hydrogen, alkalimetals, and alkaline earth metals, n represents the valence of M, and pand q each represent a molar ratio and are chosen within the ranges of0.3≦p≦3.0, q≧10, and giving a principal X-ray diffraction pattern asshown in Table 1, below:

                  TABLE 1                                                         ______________________________________                                        Lattice Spacing d (Å)                                                                         Relative Intensity                                        ______________________________________                                        11.31 ± 0.2      strong                                                    10.92 ± 0.2      very strong                                               7.83 ± 0.2       medium                                                     4.51 ± 0.15     very strong                                               4.24 ± 0.1       strong                                                    3.89 ± 0.1       strong                                                    3.73 ± 0.1       medium                                                    3.69 ± 0.1       very strong                                               3.61 ± 0.1       very strong                                                3.53 ± 0.07     medium                                                     3.43 ± 0.07     strong                                                     2.52 ± 0.05     medium                                                    ______________________________________                                    

which process consists essentially of reacting an aqueous mixtureconsisting essentially of (a) a silica source, (b) an alumina source,(c) an alkali metal and/or alkaline earth metal source, and (d) ethyleneglycol in the following molar ratios: silica/alumina≧10/1, ethyleneglycol/water=0.05/1 to 10/1, ethylene glycol/silica=5.5/1 to 10/1,hydroxyl ion/silica=0.01/1 to 0.5/1 excluding hydroxyl ions resultingfrom organic bases, at a temperature of 100° to 300° C. until thedesired crystalline silicate is formed.
 2. A process as claimed in claim1, wherein the X-ray diffraction pattern is as shown in Table 2 below:

                  TABLE 2                                                         ______________________________________                                        Lattice Spacing d (Å)                                                                      Relative Intensity                                           ______________________________________                                        11.31 ± 0.2   strong                                                       10.92 ± 0.2   very strong                                                  10.03 ± 0.2   weak                                                         7.83 ± 0.2    medium                                                        6.08 ± 0.15  weak                                                          5.61 ± 0.15  weak                                                          5.24 ± 0.15  weak                                                          4.90 ± 0.15  weak                                                          4.51 ± 0.15  very strong                                                  4.42 ± 0.1    weak                                                         4.24 ± 0.1    strong                                                       4.14 ± 0.1    weak                                                         3.89 ± 0.1    strong                                                       3.73 ± 0.1    medium                                                       3.69 ± 0.1    very strong                                                  3.61 ± 0.1    very strong                                                   3.53 ± 0.07  medium                                                        3.43 ± 0.07  strong                                                        3.32 ± 0.07  weak                                                          3.16 ± 0.07  weak                                                          2.97 ± 0.07  weak                                                          2.83 ± 0.05  weak                                                          2.52 ± 0.05  medium                                                       ______________________________________                                         Irradiation: Cu--K.sub.α                                                Wavelength: 1.5418                                                       


3. The process of claim 1 wherein M is sodium.
 4. The process of claim 1wherein M is potassium.
 5. The process of claim 1 wherein M is calcium.6. The process of claim 1 wherein said crystalline silicate has theformula 0.9Na₂ O.Al₂ O₃.74.OSiO₂.
 7. The process of claim 1 wherein saidcrystalline silicate has the formula 0.8Na₂ O.Al₂ O₃.76.OSiO₂.
 8. Aprocess as claimed in claim 1, wherein said ethylene glycol/silica molarratio is about 6.6-6.7/1.